Monoazo pigments containing a phenylamino-quinazoline radical

ABSTRACT

Monoazo pigments of the formula   WHEREIN R represents hydrogen, an alkyl or aryl group, R1 represents a hydroxynaphthalene radical in which the azo, hydroxy and carbonyl groups are in the 1,2,3-position, or the radical of the formula   R2 represents a benzene or naphthalene radical which contains a five- or six-membered hetero ring bound by condensation, X and Y represent hydrogen, halogen, lower alkyl or alkoxy groups, and X1 and Y1 represent hydrogen, halogen, lower alkyl, alkoxy or alkoxycarbonyl groups or trifluoromethyl or cyano groups, whereby in ring A the azo and amino groups are in the m- or p-position with respect to each other are prepared. The pigments may be used for pigmenting high-molecular organic materials, such as, cellulose, ethers, polyesters, alkyd resins and polycarbonates.

United States Patent 1 Mory et al.

[ July 29, 1975 1 MONOAZO PIGMENTS CONTAINING A PI-IENYLAMINO-QUINAZOLINE RADICAL [75] lnventors: Rudolf Mory, Dornach; Rolf Miiller,

Aesch, both of Switzerland [73] .Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: Aug. 3, 1973 [21] .Appl. No.2 385,617

[30] Foreign Application Priority Data Aug. 17, 1972 Switzerland 12197/72 [52] US. Cl 260/154; 106/288 Q; 117/123 C; 117/1388 R; l17/l38.8 UA; 117/1388 D;

117/140; 260/37 R; 260/37 SB; 260/37 N;

260/37 PC; 260/40 R; 260/40 P; 260/4 TN; 1260/4221; 260/140; 260/250 P; 260/251 Q; 260/307 A. 260/309.2 A; 260/310 C [51] Int. CL... C09b 29/32; C09b 29/36; D06p 1/04 [58] Field of Search 260/154 [56] References Cited UNITED STATES PATENTS 3,113,938 12/1963 Nakaten et al. 260/204 3,116,278 12/1963 Gross et a1 260/154 X 3,118,870 1/1964 Dietz et al. 260/154 3,154,532 10/1964 Weidinger et a1. 260/154 3,336,283 8/1967 Weissauer 260/154 3.711.461 1/1973 Pretzer et al. 260/154 3,719,657 13/1973 Hama et al. 260/154 Primary Examiner-Floyd D. Higel Attorney, Agent, or Firm-Vincent J. Cavalieri [57] ABSTRACT Monoazo pigments of the formula wherein R represents hydrogen, an alkyl or aryl group, R represents a hydroxynaphthalene radical in which the azo, hydroxy and carbonyl groups are in the 1,2,3- position, or the radical of the formula COCH 8 Claims, N0 Drawings MONOAZO PIGMENTS CONTAINING A r contains a fiveor six-membered hetero ring bound by PIIENYLAMINO-QUINAZOLINE RADICAL condensation, X and Y representhydrogen, halogen,

lowen alkyl or alkoxy groups, and X, and Y, hydrogen,

It has been found that new monoazo pigments of the halogen, lower alkyl, alkoxy or alkoxycarbonyl groups formula 5 or trifluoromethyl or cyano groups, whereby in ring A the azo and amino groups are in the mor p-position with respect to each other, by the coupling of a diazo compound or diazoamino compound of an amine of the 1 formula X Y X (III) NN-R --CONI-IR 1 NH are obtained, wherein R represents hydrogen, a lower R NH alkyl or aryl group, R represents a hydroxynaphtha- Y lene radical in which the azo, hydroxy and carbonyl group are in the 1,2,3-position, or the radical of the forth a'coupling component of the formula :mula

, R CONHR In the given and subsequent definitions, the term i (m lower before alkyl denotes that the substituents assi ned to it contain l to 6 carbon atoms.

Of particular interest are monoazo pigments of the R represents a benzene or naphthalene radical which formulae on com; 5 IV I NH N=N 1 2 R and I V N-N- ca-cona- R5 1 coca wherein R, X, Y, X, and Y have the above given meanings, and of R R, and R each two adjacent radicals form a condensed heterocyclic ring containing one or two groupings of the formula NHCO and the third radical, as well as X represents hydrogen, halogen, lower alkyl or alkoxy groups or nitro groups, and

Z represents hydrogen, halogen or the met'h'oxy or cyano group.

The radicals R and R, or R and R forming a heterocyclic ring bound by condensation correspond preferably to the following ring members l. N O

wherein R and R represent hydrogen or lower alkyl groups. In particular, R represents hydrogen and R the methyl g up. I

The following are given as examples of the diazo components known per'se:

' 4-(3-amino-phenylamiho)-quinazoline,

'4-(3 -amii1'o'-phenylamino )-6- or -7- chloroquinazoline,

4-( 3 '-amino-6'-methyl-phenylamino )-quinazoline,

4-( 4'-amino-phenylamino)-quinazoline,

4-( 4-amino-phenylamino)-6- or -7 be additionally substituted by, for example, a 2-methyl group or 2-phenyl group.

Instead of the diazonium salts, it is also possible to use the corresponding diazoamino compounds. These are obtained, using a known process, by coupling of an aryldiazonium salt with a primary or, preferably, secondary amine. A wide variety of amines are suitable for this purpose; examples are: aliphatic amines, such as methylamine, ethylamine, ethanolamine, propylamine, butylamine, hexylamine, and particularly dimethylamine, diethylamine, diethanolamine, methylethanolamine, dipropylamine or dibutylamine, aminoacetic acid, methylaminoacetic acid, butylaminoacetic acid, aminoethanesulphonic acid, methylaminoethanesulphonic acid, B-aminoethylsulphuric acid; alicyclic amines, such as cyclohexylamine, N-methylcyclohexylamine, dicyclohexylamine; aromatic amines, such as 4-aminobenzoic acid, sulphanilic acid, 4-sulpho-2- aminobenzoic acid, (4-sulphophenyl)guanidine, 4-N- methylaminobenzoic acid, 4-ethylami nobenzoic acid,

l-aminonaphthalene-4-sulphonic acid, 1- aminonaphthalene-2,4-disulphonic acid; heterocyclic amines, such as piperidine, morpholine, pyrrolidine, dihydroindole and, finally, also sodium cyanamide or dicyandiamide.

As a rule, the diazoamino compounds obtained are difficultly soluble in cold water, and can be separated, optionally after salting out, in crystalline form from the reaction medium. In many cases, the moist press cakes can be employed for the further reaction. In certain cases, however, it can prove advantageous to remove the water from the diazoamines by vacuum drying prior to the reaction.

The coupling of the diazoamino compound with the coupling component is performed in an organic solvent, c.g. chlorobenzene, o-dichlorobenzene, nitrobenzene, pyridine, ethylene glycol. ethylene glycol monoethyl or -monomethyl ether, dimethylformamide, formic acid or acetic acid. With the use of solvents miscible with water, it is not necessary to employ the diazoamino compounds in the anhydrous form. The aqueous-moist, suction-filtered press cakes, for example, can be used.

The coupling is advantageously performed hot, preferably at a temperature of between and C, in an acid medium, and is very rapid and, moreover, complete. If neutral solvents are used, then the addition of an acid, e.g. hydrochloric acid, sulphuric acid, formic acid or acetic acid, is of advantage. By virtue of their insolubility, the pigments obtained can be isolated from the reaction mixture by filtration. An aftertreatment with an organic solvent, which is necessary in the case of pigments obtained by aqueous coupling means, is there-fore not required in most cases.

Applicable coupling components are 2,3- hydroxynaphthoic acid arylides or acetoacetic acid arylides wherein R in formula I represents a benzimidazolone, benzoxazolone, indazolone, phenmorpholone, naphthostyryl, naphthalimide, quinolone, quinazolone, 2,4-dihydroxyquinazoline, 2,3-dihydroxyquinoxaline or l,4,-dihydroxyphthalazine radical.

The following coupling components are given as examples:

5-(2,3'-hydroxynaphthoylamino)-benzimidazolone,

l-methyl-5-( 2,3 -hydroxynaphthoylamino benzimidazolone,

5-(2',3'-hydroxynaphthoylamino)-6-methylbenzimidazolone,

l-( 3 '-chlorophenyl )-5-( 2',3'-hydroxynaphthoylamino)-benzimidazolone, 5-ethoxy-6-(2',3'-hydroxynaphthoylamino)- benzimidazolone, 5-(2,3'-hydroxynaphthoylamino)-benzoxazolone, 7-(2',3'-hydroxynaphthoylamino)-phenmorpholone- 6-methyl-7-(2,3'-hydroxynaphthoylamino)-phenmorpholone-( 3 4-(2,3'-hydroxynaphthoylamino)-naphthostyryl, 4,6-dimethyl-7-( 2,3 '-hydroxynaphthoylamino quinolone-(Z),

6-(2',3'-hydroxynaphthoylamino 1 ,2,3,4-

tetrahydro-quinazoline-dione-(2,4),

6-(2',3"-hydroxynaphthoylamino)-l ,2,3,4-

tetrahydro-quinoxaline-dione-( 2,3),

S-acetoacetylamino-benzimidazolone,

4-methoxy-5-acetoacetylamino-benzimidazolone,

4-ethoxyS-acetoacetylaminc-benzimidazolone,

4-methyl-5-acetoacetylamino-benzimidazolone. 4-chloro-S-acetoacetylamino-benzimidazolone, l-methyl-5acetoacetylamino-benzimidazolone, l-ethyl-5-acetoacetylamino-benzimidazolone. l-n-propyl-S-acetoacetylamino-benzimidazolone,

l -iso-propyl-5-acetoacetylamino-benzimidazolone,

l-n-butyl-5-acetoacetylamino-benzimidazolone,

l -cyclohexyl-5-acetoacetylamino-benzimidazolone.

l-phenyl-S-acetoacetylamino-benzimidazolone,

l 3 -chlorophenyl )-5-acetoacetylaminobenzimidazolone,

l 4'methylphenyl )-5-acetoacetylaminobenzimidazolone,

l-methyl-S-acetoacetylamino-6- chlorobenzimidazolone,

5-acetoacetylamino-benzoxazolone,

5-methyl-6-acetoacetylamino-benzoxazolone,

5-chloro-6-acetoacetylamino-benzoxazolone,

5-acetoacetylamino-indazolone,

lS-acetoacetylamino-phenmorpholone-(3),

Tl-acetoacetylamino-phenmorpholone-( 3 6-acetoacetylamino-8-chloro-phenmorpholone-( 3 b-chloro-l'acetoacetylamino-phenmorpholone-( 3 b-methyl-Tl-acetoacetylamino-phenmorpholone-( 3),

tS-methoxy-V-acetoacetylamino-phenmorpholonel-acetoacetylamino-naphthostyryl,

3-acetoacetylamino-naphthalimide,

4-methyl-7-acetoacetylamino-quinolone-(2),

4,6-dimethyl-7-acetoacetylamino-quinolone( 2 4-methyl--acetoacetylamino-7-chlor0quinolone- 6-acetoacetylamino-3 ,4'dihydro-quinazolone-(4),

7-acetoacetylamino-3 ,4-dihydro-quinazolone-(4),

5-acetoacetylamino-6-chloro-3,4-dihydroquinazolone-( 4),

6-( 4 '-acetoacetylamino-benzoylamino )-3,4-dihydroquinazolone-(4),

b-( 3 -acetoacetylamino-4'-methoxy-benzoylamino)- 3 ,4-dihydro-quinazolone-( 4),

TM 3 '-acetoacetylamino-4-chlorobenzoylamino)- 3 ,4-dihydro-quinazolone-( 4 2-( 4'-acetoacetylamino-phenyl )-3 ,4-dihydroquinazol0ne-(4),

3-( 3 -acetoacetylamino-phenyl)-3,4-dihydroquinazolone-( 4 Z-t 3'-acetoacetylamino4'-methyl-phenyl )-3,4-dihydro-quinazolone-( 4),

2-( 3'-acetoacetylamino-4-methoxy-phenyl )-3,4-

dihydro-quinazolone-( 4),

2-( 3'-acetoacetylamino-4'-chlorophenyl )-3,4-dihydro-quinazolone-( 4 2-( 3 '-acetoacetylamino-4'-chlorophenyl )-6-chloro- 3 ,4-dihydro-quinazolone-(4),

b-acetoacetylamino-l ,2,3,4-tetrahydroquinazolinedione-( 2,4

'l-acetoacetylaminol ,2,3 ,4-tetrahydro-quinazolinedione-( 2,4),

b-acetoacetylaminol ,2,3.4-tetrahydro-quinoxalineldione-( 2,3

S-acetoacetylaminol ,2,3,4-tetrahydro-phthalazinedione-( 1,4).

The aforementioned coupling components are.

known compoundsv The coupling is advantageously effected by the gradual addition of the aqueous-alkaline solution of the coupling component to the acid solution of the diazonium salt, and is preferably performed with a pH-value of 4-6.

The pH-value is advantageously adjusted by addition of a buffer. Suitable buffers are, e.g. thesalts, especially alkali salts, of formic acid, phosphoric acid or; in particular, of acetic acid. The alkaline solution of the coupling component advantageously contains a wetting, dispersing or emulsifying agent, for example, an aralkylsulphonate such as dodecylbenzenesulphonate, or the sodium salt of l,l'-naphthy lmethanesulphonic acid, polycondensation products of alkylene' oxides such as the resultant product of the reaction of ethylene oxide with p-tert.-octylphenol, also alkyl esters of sulphoricinoleates, e.g. n-butylsulphoricinoleate. The dispersion of the coupling component can advantageously also contain protective colloids, e.g. methylcellulose, or small amounts of inert organic solvents difficultly soluble or insoluble in water, e.g. optionally halogenated or nitrated aromatic hydrocarbons, such as benzene, toluene, xylene, chlorob enzene, dichlorobenzenes or nitrobenzene, as well as aliphatic halogenated hydrocarbons such as, e.g. carbon tetrachloride or trichloroethylene; and also watermiscible organic solvents such as acetone, methyl ethyl'ketone, methanol, ethanol or isopropanol, particularly dime thylformamide. 3 l 1 The coupling can be advantageously performed also by a process in which an acid solution of the diaionium salt is continuously combined, in a mixing nozzle, with an alkaline solution of the coupling component,

whereby an immediate coupling of the components occurs. The resulting dyestuff dispersion is continuously taken from the mixing nozzle, and the dyestuff separated by filtration.

The new dyestuffs constitute valuable pigments which, in a finely divided form, can be used for the pigmenting of high-molecular organic material, e.g. cellulose ethers and cellulose esters, superpolyamides or superpolyurethanes or polyesters, acetyl cellulose, nitrocellulose, natural resins or synthetic resins, such as polymerisation resins or condensation resins, e.g. aminoplasts, especially ureaand melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefins such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid ester, rubber, casein, silicone and silicone resins, singly or in admixtures.

It is immaterial in this connection whether the mentioned high-molecular compounds are treated as plastic masses or melts, or in the form of spinning solutions, lacquers or printing pastes. Depending on the purpose of application, it proves advantageous to use the new pigments as toners, or in the form of preparations.

Where not otherwise stated, the term parts in the following examples denotes parts by weight; percentages are given as per cent by weight, and temperatures are expressed in degrees Centigrade.

EXAMPLE 1 A monoazo pigment having excellent fastness to migration and light and corresponding to the formula COCl-l 01-1 is obtained by a process in which 3 parts of 4-(2- methoxy-4'-amino-5'-chl0ro-phenylamino)- quinazoline in 50 parts by volume of ice water is diazotised with 2.5 parts by volume of lON hydrochloric acid and 2.5 parts by volume of 4N sodium nitrite solution. The diazo solution is added at l0-20C, in the course of 20 minutes, to a mixture of 2.47 parts of l-methyl-S- acetoacetylamino-benzimidazolone and 3.3 parts of anhydrous sodium acetate in 100 parts by volume ofdimethylformamide. After completion of coupling, the formed pigment is filtered off, washed with hot water and with methanol and dried.

1n order to obtain a favourable colouristic form, the crude pigment is heated to boiling for minutes in 50 parts by volume of N-methyl-pyrrolidone; after cooling, it is filtered off, washed with methanol and dried. There is thus obtained an amount of 4.85 parts of a dark-orange pigment powder, which produces in polyvinyl chloride an orange shade having excellent fastness to migration and to light.

The starting materials can be prepared as described N -CO in Example 1 of the German Patent Specification No. 1,138,318, or of the corresponding US. Pat. No.

EXAMPLES 2-4 Similarly good results are obtained by employing, instead of the diazo component of Example 1, 4-(4'- amino-2',5-dimethoxy-phenylamino)-quinazoline, 4-

coloured pigments are obtained, and'in the third case,

a yellow pigment.

EXAMPLES 5-38 In the following table are listed further pigments which were obtained in the described manner. Column 1 contains the diazo component, column [I the coupling component, and column 111 the shade of the polyvinyl chloride dyed with the pigment.

5 4-(4'-Amino-2 ,5 -dimethoxy- 5-( 2 -Hydroxy-3 -naphthoylviolet phenylamino )-quinazoline amino )-benzimidazolone 6 4-(4'-Amino-2'-methoxy-5 rediole chlorophenylamino-quinazoline 7 5-Acetoacetylamino-benzimiorange dazolone 8 4-( 4'Amino-2 '-methoxy-5 5-( 2 '-.Hydroxy-3 '-naphthoylred-violet methylphenylamino )-quinazoline amino )-benzimidazolone 9 5-( 2'-Hydroxy-3 -naphthoylblue amino )-6-me!hyl-benzimi dazolone l0 l-Methyl-5-( 2 '-hydroxy-3 grey-blue naphthoylumino l-henzimidazolonc l l 5-( 2'-Hydroxy-3 '-naphthoylred-violet amino )-6-chloro-benzimidazolone 12 4-(4'-Amino-2,5'-diethoxy- 5-(2'-Hydroxy-3'-naphlhoylviolet phenylamino )-quinazoline amino )-benzimidazolonc l3 4-( 4 '-Amino-2'-mcthoxy-5 4-M ethyl-6-phenoxy-7-acetoorange methylphenylamino )-quinaacetyl-amino-quinolone-( 2) zoline 14 4-( 4'-Amino-2'-methoxy-5'- 4-Methyl-6-acetoacetylbrownmethylphenylamino )q uinaamino-7-chlor0-quinolone-( 2) orange 20 me 15 4,6-Dimethyl-7-acetoacetylyellow amino-quinolone-( 2) 16 o-Acetoacetylamino-quinared-ye11ow zolone-( 4) 17 6-Acetoacetylamino-quinared-orange zoline-dione-( 2,4)

18 5-Acetoacetylamino-6 chloroorange benzimidazolone l9 6-( 2'-l-lydroxy-3 '-naphthoylbluc-violet amino)- uinazoline-dione-(2,4)

20 4-Methy 7-(2'hydroxy-3'- blue-violet naphthoylamino )-quinolone-( 2) 21 4-( 4 '-Amino'2 ,5 '-dicthoxy- 1-Methyl-5-acetoacctylaminored orange phenylamino)-quinazoline benzimidazolone 22 4-(4'-Amino-2,5'-dimcth- -Methyl-7-acctoucctylaminoyellow oxyphcnylamino l-quinazolinc phcnmorpholone( 3) 23 4-(4'-Amino-2-mcthoxy-5- 7-( 2-Hydroxy-3'-naphthoylbrownchloro-phcnylamino)-quinaamino)-phcnmorpholonu-( 3) violet Zolinc mcthyl-phcnylamino)-quinazolinc ('ontinued lll g I S-Acctoacetylamino benzimidazolonc naphthoylamino )-phenmorpholone-( 3 5-( 2 '-Hydroxy-3 '-nuph!hoylamino)-benzimidazolone 6-M ethyl-7-acetoacetylamino-phenmorpholone-( 3) S-Acetoacetylamino-be nzimidazolone 7-( 2 "Hydroxy-3 '-nap'hthoylamino )-phenmorpholon-( 3) 6M ethyl-7-( 2 '-hydroxy-3 naph'thoylainino )-phenmrpholone-( 3 S-Acetoacetylamino-bengimidazolone 6-Methyl-7-acetoacetylamino-phenmorph0lOn-( 3) 2 '-Hyz :lroxy-3 '-naphthoylamino )-benzimidazolone 6-Methyl-7-acetoacetylaminophenmorpholone-( 3) 6-Methyl-7-( 2 "hydroxy-3 naphthoylamino )-phenmorpholone-( 3 5-( 2 '-Hydroxy-3 '-naphthoylamino )-benzimidazolone orange yellow red claret shade green-yellow green-yellow blue blue

red-orange green-yellow maroon shade yellow r'ed violet I. A monoazo pigment of the formula wherein R ishydrogen, lower alkyl or phenyl, X and are hydrogen chloro, lower alkyl or lower alkoxy, X 1 and Y are hydrogen, chloro, lower alkyl, lower alkoxy, lower alkoxycarbonyl, trifluoromethyl or cyano, R and R or R and R together form a heterocyclic ring of the formula wherein R and R is hydrogen or lower alkyl. X is hydrogen, chloro, lower alkyl, lower alkoxy or nitro and Z is hydrogen, chloro, methoxy or cyano.

3. Monoazo pigment according to claim 2 of the formula wherein R is hydrogen, lower alkyl or phenyl, X and Y are hydrogen, chloro, lower alkyl, lower alkoxy, X, and Y, are hydrogen, chloro, lower alkyl, lower alkoxy, X Y

lower alkoxy carbonyl, trifluoromethyl or cyano, R X and R or R and R together form a heterocyclic ring of the formula 1 1 N MI 1 -CO l| (Vl) R -NR., Y

wherein R and R is hydrogen or lower alkyl, X is hydrogen, chloro, lower alkyl, lower alkoxy or nitro, and I Z is hydrogen, chloro, methoxy or cyano. N Co 2. A monoazo pigment of the formula V i N-CH-CONH- NR6 wherein R and R is hydrogen or lower alkyl.

4. Monoazo pigment according to claim 2 of the formula 

1. A MONOAZO PIGMENT OF THE FORMULA
 2. A monoazo pigment of the formula
 3. Monoazo pigment according to claim 2 of the formula
 4. Monoazo pigment according to claim 2 of the formula
 5. Monoazo pigment according to claim 2 of the formula
 6. Monoazo pigment according to claim 2 of the formula
 7. Monoazo pigment according to claim 1 of the formula
 8. Monoazo pigment according to claim 1 of the formula 